Diallyl esters and polymers thereof



Patented Mar. 13, 1951 7 UNITED STATES" PATENT OFFlCE 2,545,184 DIALLYL ESTEBS AND roLYMEns THEREOF .Lynwood N, Whitehill, Berkeley, and Edward C.

Shokal, Oakland, Calif ass'ignors to Shell Dcvelopment Company, San Francisco, Calit, a,

corporation of Delaware No Drawing. Appli onne 11,. 1945.

Serial No.15985894 and the association of several desirable properties in a single synthetic resin has been largely instrumental in determining its accepta ility for usage .on a commercial scale. :In recent years,

resinous polymers from a variety of types ofaallyl esters have been described in patents and journal articles. Many of these resinous al yl'ester polymers have propertie which appear-to make them attractive for utilization on a commercial scale, Thus, some allyl esters give resinous poly- :mers which are infusible, hard solids as well as being transparent so vthat'they could be usedas substitutes for glass. However, in order to be satisfactory for thispurpose, it is vitally necespr perties without also having undesirable properties as are possessed with previously known closely related compounds. The compounds of the invention accordingly provide polym ric res- -ins of great utility because the resins possessa combination or desired pr perties without sacrifine in other respects, 1

The compounds of the invention are bietagla'mn1a-monoo1efiriic .mono'hydric alcohol neutral esters of a hydroxy aliphatic dicarboxylic acid having the .hydroxy groups of the acid esteriiied with saturated aliphatic monocarl oxvlic acids. The compounds include neutral esters oithe formula NIRAGQUhih I soon wherein R1 a monovalent saturated aliphatic hydrocarbon radical, R2 is an aliphatic hydrocarbon radical, Re and are the hyorocarbo "atoms contained R2.

the invention, tartarate diacetate is .a typlweal member] and is also particularly preferred 'since the intermediates used'i-n its preparation are dric alcohol, and in is an integer not greater than the number of carbon atoms contained in "R2. Preferably, R1 contains not more than 3 carbon atoms and R2 also contains not more than 6 carbon atoms. TR; and R4 are most preferably :a'llyl radicals. When the ester is one with R2 containing not mor than 6 carbon atoms, at is preferably an integer not greater than 4, but "in any case not greater than the number or carbon Qt the compounds of readily'avai'lalble in commercial markets. The compound. has the ,tormula Q=Q1OQH2QH =C3H3 (311 6 0 0 H cmpooj H coo-enrolment This compound can be olymerized to a hard.

in one or more other respects. Thus polymeric di lyl p hailate is a hard, ough resin but is lacking in light stability. While the resin when r t pr pared is subs antially water-white in c019 it becomes in rather a short time noticeably y llow and this discoloration impair i transparency so as to 'bar its suitability for many uses. tendency to discolor is a fault of many allyl ester resins. Polymeric diallyl tartrate diacetate, on the other hand, has excellent light stability as well asjbeing a hard, tough resin. Polymeric diallyl succinat is another material closely related to those of the invention. This material is of little general utility for the reasonthat the polymer So lacking in strength that the usual routine physical tests used commercially cannot even be performed upon it, and consequently it has no practical use. Likewise,

, polymeric diallyl tartrate is a resin of desirable hardness and toughness as :well as having good "light stability, but the resin is deficient in resistance toward water and chemicalreagents. It

absorbs appreciable quantities of water and in oi a b tasamma-inonooleflnic monohrso tact with water, dilute acids or dilute alkalies.

It has also been suggested heretofore to react diallyl tartrate with a mixture of succinyl and adipyl chlorides. The product obtained from this reaction is in the nature of an alkyd resin. The mixture of succin l and adipyl chlorides react with the free hydroxy groups of the diallyl tartrate so that a very viscous to solid polyester is formed. While this alkyd material can be poly-' merized by carbon-to-carbon bonding through the allyl groups, it is lacking in an important property. The polymer is opaque and has no transparency. Furthermore, the product before polymerization is a solid or very viscous substance and consequently cannot be used for the manufacture of reinforced articles such as laminates. of paper or fabrics since these cannot be impregnated or immersed in the resin forming product without the use of solvents. In commercial practice the use of solvents is ordinarily prohibited because of unduly complicating" the manufacture of the laminates.

Diallyl tartrate diacetate is: a mobile liquid which flows free and is adapted .to

. impregnation of paper and fabrics by immersion in laminating operations.

Polymers of the compounds of the invention are thus seen to;possess .c; La, combination of desirable qualities Without cor- --;-responding undesirable ones and are thus "unique- -ly fitted for commercial usage.

As stated, the compounds ofthe' invention are beta.gamma-monoolefinic monohydric' alcohol jj neutral esters of a hydroxy aliphatic dicarboxylic acid having the hydroxy group or groups of the -.;.acid esterified jwith a'saturated aliphatic monocarboxylic acid. By a .neutra ester referenceis made to the compound itself in that all of the carboxylic acid groups have been esterified with the unsaturated alcohol although the bulk material ma contain traces of acid, as is usual even with highly purified esters. The compounds of the invention are probably most conveniently and .understandably described in terms of the materials used for their preparation.

' coholsv have a single olefinic double-bonded link- 40 like.

The beta,gamma-monoolefinic monohvdric alage between two carbon atoms which are in the beta and gamma positions with res ect .to the alpha carbon atom to which the single hydroxyl group is directlyilinked. These singly unsaturated alcohols contain the single olefinic linkage between two carbon atoms of aliphatic character to one of which carbon atoms is linked directly a saturated carbon atom having the hydroxyl group linked directly thereto and preferably the alcohols contain no other elements than carbon, hy- .drogen, oxygen and halogen. The alcohols can be either primary, secondary or tertiary alcohols, al-

though primary alcohols are preferred. Theycan preferably those containing up to but not more. 1 than 6 carbon atoms areu sed. Esters of a particularly suitable class of alcohols aretllos eiof -beta-alkyl-substituted allyl alcohols; e.' g. meththose from allyl alcohol.

allyl, ethallyl, etc. The most preferred esters are Some specificrepre- ;sentative examples of beta,gamma-monoolefinic monohydric alcohols used in preparation of the esters of the invention include allyl alcoho1 methally], alcohol, crotyl alcohol; tigly o o e falcohol, buten-1-o1-3, p 3'methyl' buten-l-ol-B, beta-chlorallyl alcohol, gammachlorallyl alcohol, l-bromobuten-l' ol t', Z-methylbuten-1-ol-3, cinnamyl alcohol, penten-Z-ol-l, hexen-2-ol-1,

octen-2-ol-1, decene2-ol-l', do-

2-cyclobutenol, beta-phenylallyl alcohol, betacyclohexylallyl alcohol and the like.

The esters of the invention are derivable from a hydroxy aliphatic dicarboxylic acid of which any 5 are suitable although dicarboxylic acids containing not more than 8 carbon atoms are preferred and tartaric acid is particularly preferred. lihe acid contains one or more hydroxy groups and when the radical between the carboxylic acid groups is in saturated, it preferably contains as many hydroxy groups as there are carbon atoms in the radical. Representative specific examples of the class are such acids as tartronic, malic, isornalic or methyltartronic, citramalic or alpha-methylmalic, ethyll5 tartronic, propyltartronic, beta-hydrcxyisomalic,

.contain any number of carbon atoms,- ..although beta-methylmalic, beta,beta-dimethylmalic, alpha,beta-dimethylmalic, beta-ethylmalic, alpha, beta methylethylmalic, trimethylmalic, isopropylmalic, gamma,delta-dihydroxy propyl- 20.1nalonic, tartaric, beta-hydroxyglutaric,..alpha,

gamma-dimethyl-beta-hydroxyglutaric, alpha, beta dihydroxyglutaric, alpha,garnma dihydroxyglutaric, alpl1a,gamrna dihyzlroxy alpha, gamma dimethylglutaric, alpha,gamma dihy- "23 droxy beta,beta {dimethylglutaria trihydr'oxy- 'glutaric, alphamethylrtrihydroxyglutaric, alphali'ydroxyadipic, alpha-,alphaedihydroxyadipic, trihydroxyadipic, tetrahydroxyadipic or. saccharic,

mannosaccharic, .idosaccharic, mucic, talomucic,

so alphahydroxy+alpha-methyladipic, beta-methylbeta-hydroxyadipic, alpha,alpha gamma 'tri- -.methyl beta 'hydroxyadipic, pentahydroxypimelic, alpha,alpha'-dihydroxysuberic, and the like. 7

In thecompounds of the invention, the hydroxy groups of the hydroxy aliphatic dicar .boxylic acid have been esterified with a saturated aliphatic monocarboxylic acid. Any saturated aliphatic monocarboxylic acid can be used in- 40 eluding such representative saturated acids as the carboxylic acid group linked to a monova-lent saturated aliphatic hydrocarbon radical. It is desirable that the saturated aliphatic monocarboxylic acid contain not more than 7 carbon atoms, and preferably, saturated fatty acids of not more than 4 carbon atoms are used ofwhich acetic acid is most preferred.

The compounds of the invention can-be prepared by any suitable method. Preferably, a two step esterification process is used. The unsatu- G ratedalcohol is first esterifiedwith the hydroxy dicarboxylic acid and this ester is then esterified "with .the: saturated monocarboxylic acid. The firstfstep is effectedby heating a mixture'of the unsaturated alcohol] and hydroxy dicarboxylic '6 acid'along With an esterificationjcatalyst and a water-entraining agent in a vessel fitted withfa fractionating column. The water of reaction'is removed substantially as fast as formed with the aid of the Water-entraining agent which distile the water as an azeotrope from the reaction mixture. When the esterification is complete, the mixture is subjected to distillation preferably under reduced pressure to remove volatiles, but 5 the formed ester is not takenoverheadas disdecen-Z-ol-l, tetradecen-2-ol-1, 2 'cyc1ohexenol, tillat. Instead, the saturated monocarbpxylic -acid is added along with water-entraining agent and-if desired more esterification catalyst. Heating of the reaction mixture is then resumed with removal of water" of reaction" formed by the [second reaction. When the reaction is complete in this second step, the'catalyst is neutralized and the reaction mixture is preferably subjected to distillation and purification of the product. The desired ester is taken over as distillate except when too high boiling. Various substances are suitable as esterification catalyst like "sulfuric acid, phosphoric acid, benzene sulfonic acid, zinc chloride andthe like. Excellent results are ob- ,tained with p-toluen'e sulfonic acid as catalyst. ;The water-entraining agent is a substance of {lower boilingpoint than the unsaturated alcohol and 'it has the ability to form an azeotrope with water which will separate into two layers on "cooling". Hydrocarbons like benzene, toluene, xylene,- octane, decane, ethers like diisopropyl ether, dibutyl ether, diamyl ether, are suitable.

Iri'preparin'g the esters of the invention, it may yin some cases be desirable to use as reactants the lactone of the hydroxydicarboxyli'c. acid. The anhydride of the saturated monocarboiwlic acid "alsoprovides aniore rapid and complete reaction than the free acid. When the beta,gamma-monoolefinic monohydric alcohol is one containing an :unsaturated tertiary carbon atom directly linked il'inked directly thereto as is the case with methj'allyl alcohol, for example, it may be desirable to employ a different method of production since "such alcohols tend to rearrange in the presence fof acids like the estcrificationcatalyst. To avoid this difficulty, the ester can be prepared by reacting the corresponding chlorides or bromides of the unsaturated alcohol with the sodium or potassalt of the hydroxy dicarboxylic acid. An- "other method is to employ an alcohol-exchange process wherein the methyl or ethyl ester of the hydroxy dicarboxylic acid is reacted with the unsaturated alcohol. These methods can of course be applied to preparation of all members of the series, if desired.

The compounds of the invention from acids having more than one hydroxy groups can have the groups e'sterified with different monocarboxylic acids, if desired. Thus a mixed tartrate ester can be prepared by reacting equimolal amounts of diallyl tartrate with propionic anhydride so that diallyl tartrate monopropionate is obtained. This compound is then reacted with acetic anhydride whereby diallyl tartrate monoacetate monopropionate is produced. Although it is'most desirable to have all of the hydroxy 'groups of the hydroxy polycarboxylic acid esteri- 'fied with the monocarboxylic acids, the invention contemplates compounds wherein part of the hydroxy groups remain unesterified.

It may also be desirable to employ a polymeri'zation inhibitor when the esters'of the invention are prepared. For this purpose tannic acid is "particularly suitable. If desired, other inhibitors "such as pyro'gallol, hydroquinone, aniline, phenyl- {en'e-diamine, sulfur; 'thiophenol, or the like can be used. I I 'The following" examples are g ven for thepurf'po'se of illustrating the methods of production and some properties of the esters.

EXAMPLE I '.'to the carbon atom having the hydroxyl group "toluene sulfonic acid as catalyst. The water of reaction was removed as distillate with the aid of benzene as water-entraining agent. After about 20 hours heating, the reaction was complete and the volatiles were removed by distillation under reduced pressure. An analysis of a sample of the crude ester gave a saponification value of 0.934 eq. per 100 grams. The theoretical value is the same.

EXAMPLE II .4% acetic acid.

Theoreti- Found cal Carbon, per cent I 55. 5 56.1 Hydrogen, per cent 6; 3 6. 3 Saoonificatiqn value, eq. per 100 grams 1. 18 1.17 Acidity to poenclphthalein, eq. per 100 grams. 0. 07 0.0 Specific gravity, 2 4 l. 1305 Refractive index, 20/D 1. 4509 Treatment of the product with anhydrous potassium carbonate and redistillation reduced the acidity to about 1.8% acetic acid. The ester 'boiled at 94. C. under 0.8 mm. Hg pressure. I

,\ EXAMPLE III Diallyl malate stearate was prepared from diallyl malate obtained as described in Example I. About 107 grams of the crude diallyl malate and 142 grams of stearic acid were heated with 2 grams of p-toluene sulfonic acid and 1 gram of zinc chloride. The water of reaction was removed azeotropically using benzene. The esterification required about 18 hours to reach completion whereupon the resulting solution was poured into a liter of hot methyl ethyl ketone and filtered with the aid of decolorizing charcoal. The filtrate was chilled to 0 C. and the precipitated stearic acid removed by filtration. The methyl ethyl ketone was evaporated from the filtrate leaving 165 grams of material (68.8% conversion) which the following analysis shows contained considerable stearic acid:

Theoretical fei- 'Found St came l Ester Acid Carbon, per cent l- 71. 4 70.0 .76. 2 .Hydrogen. per cent 11. ll0. 8 l2. 7 Bromine "o., gm. Br. per 100 gm 29 0 Acidity. eq. per gms. 0. 003 0.0 0.35

Specific gravity. 20/4... 0. 941 Refractive index, 20/D 1'. 456' Diallyl'tartrate was prepared from d-ta'rta-ric acid using 600 grams of acid, 940 gr'ams of allyl alcohol, 3 grams of 'm-toluene sulfonic acid as catalyst and 200 cc. of benzene to remove the water of reaction as the azeotrope. The reaction required about 20. hours for completion after which the materials boiling tiIJtQ'fllO; ..Q..under "7 l5 mmJHgIpi-esSure were removed. A residue" of .861 grams of crude diallyl tartrate was obtained corresponding to 93.6% conversion. Analysis of the product given below indicated it was about 97% pure:

Theoreti- Found cal Saponification value, eq. per 100 gms 0. 862 0. 870 Acidity to phenolphthalein, eq. per 100 grns 0.09 0.

EXAMPLE V washed with dilute sodium hydroxide and then -with water. The chloroform was flashed off and the product distilled in vacuo whereby about 142 grams of, the ester boiling at 127 C. under 0.4

mm. pressure were obtained. An analysis of the product gave the following results:

Found is? Carbon, percent 52. 2 53. 5 Hydrogen, per cent' 5. 8 517 Sapomfication value, eq. per 100 gms 1. 26 1 27 Acidity, eq. per 100 grrns 7 0.007 0.0 Specific gravity, 20/4 1. 1672 Refractive index, 20/D 1.4529

EXAMPLE VI The preparation of diallyl tartrate diacetate was repeated using acetic anhydride as acetylating agent. About 640 grams of diallyl tartrate, 1 gram of p-toluene sulfonic acid as catalyst and 1 gram of tannic acid as polymerization inhibitor were heated on a steam bath and 830 grains of acetic anhydride was added dropwise. Heating was continued several hours and then the reaction mixture was distilled whereby about 787 grams of diallyl tartrate diacetate boiling at 130 C. under 0.5 mm. Hg pressure was obtained. This corresponds to a conversion of 91.5%. An analysis of the water-white product gave the following results:

Theoret- Found ical isaponification value, eq. per 100 gms 1(26' 7 1. 27 Acidity, eq. per 100 gms O. 001 0.0 Bromine No, gramBnper 100 gms. 103 101. 5 Specific gravity, 20/4 l. 1672 'Refractive Index, 20/D 1.4529

' Found Saponification value, eq. per 100 gms 1.13 Acidity; eq. per 100 gms 0.001 Bromine N01, gram Br. per 100 gms. 96 Specific gravity, /4... 1.1233 Refractive index, 20/D. 1. 4510 EXAMPLE VIII Diallyl tartrate dibutyrate was prepared in the manner described in Example VI using about 680 grams of diallyl tartrate and 100 grams of butyric anhydride. The conversion to the ester which boiled at 164-166" C. at 0.5 mm. Hg pressure was 53%. The water-white product analyzed as fol;- lows:

Theoret- Found i631v Acidity, eq. per 100 gms 0. 002 0.0 Bromine No., gram Br. per 100 gms. 37. 2 86.5 Specific gravity, 20/4 .0916 Refractive index, 20/D 1. 4510 EXAMPLE IX d-Saccharic acid was prepared by oxidizing. glucose withnitricacid. About 278 grams of dglucose was dissolved in 850 cc. of 20% nitric acid and the solution was heated according 'to the of about 42 grams of diallyl saccharate, was a following schedule: 3% hours at to 65 C., 2 hoursat to 50 C., 8 hours at 55 to C., .8 hours at 65 to C. and 4 hours at 94 to--.C. About 12 gramsfof calcium carbonate was added to the cooled solution and, after standing overnight, the precipitate of calcium oxalate was removed, the filtrate giving no test for oxalate ion. The solution was neutralized to phenolphthalein with 30% potassium hydroxide and then evaporated at 50 C. to 430 grams under reduced pressure. The insoluble monopotassium salt of saccharic acid monolactone was formed by addition of 84 grams of acetic acid. After standing overnight, the product was collected and washed with a small quantity of cold 20% methanol. It was purified by boiling with 100 cc. of water for about20 minutes. Although all the solid did not dissolve in the hot solution, a pure white product Was obtained. The purified monopotassium salt of saccharic acid monolactone weighed about 43 grams.

EXAMPLE X Diallyl saccharate was prepared from the monopotassium salt of saccharic acid monolactone described i -Example IX. A solution of about-42 grams of the salt in 20; cc. of concentrated hydrochloric acid was treated with 500 of allyl alcohol in six separate portions. Each portion was added to the saccharic acid solution, heated and stirred vigorously, then cooled and the allyl alcohol solution of saccharic acid decanted from the precipitate of potassium chloride; Attheend of the treatment, the solution was concentrated by evaporation to a volume'of about 200 cc. -This-solution wasmixed with c.C..- Oinbenzene and'2 grams of p-toluene sulfonic acid, and was heated with removalof the water of reaction for about 26 hours. The volatile compounds were then distilled from the mixture under reduced pressure. The residue, consisting l iallyli saccharate tetra-acetate was prepared from the crude diallyl sacoharate described in Example X. About .40 grams of the esterand 1 gram of p-toluene sulfonic acid were dissolved in 150 grams of acetic anhydrideand the solution heated to about 45 C. whereupon an exothermic reaction took place so the temperature rose to 65 C. spontaneously. The solution was cooled to 50 C. and then heated gradually to reflux temperature of 132 C. over a period of 45minutes'with an additional'heatingfor 45 minutes at reflux temperature. poured into water with vigorous stirring and after standing overnight a dark oil separated which was extractedwith ether. The ether $01111 tion. was extracted with.5% sodium hydroxide.

solutionto remove acetic acid and incompletely esterified saccharic. acid. The ether was "evapm The solution was then rated from the solution leaving about 26 gramsof viscous oil comprising the *diallyl saccharate' tetra-,acetate which contained some material which was not completely esterified with acetic acid.

While the esters of the invention can be used:

- perborates, persulfates, ozone, air and oxygen.

The esters can be polymerized also in the presence of their own peroxides or their ozonides. Another class of polymerization catalysts is the di(tertiary alkyl) peroxides, notably di(tertiary butyl) peroxides as described and claimed in the copending application of Vaughn and Rust, Serial No. 48-1,052, filed March 29, 1943, now No. 2,425,476. If -desired,- mixtures crewman-,- zation catalyst can be used, a suitable mixture being that of benzoyl peroxide and ditertiary' butylperoxide as described and claimed in oopendin application, Serial No. 572,986, filed Jan-- uary 9, 1945, nowabandoned. In some cases,

it may be desirable to conduct the polymerization.

inthe concurrent presence ofboth a catalyst and an inhibitor of polymerization. The amount of catalyst used will ordinarily/be between about 0.91% and about. 5%, although it. is not necessarily limited to this range. still other cases, it may be desirable to use no other agent to efiect polymerization than. heat. Polymerization is tent.

procedures and it is characterized by being solg, uble in many common organic solvents. At 9rd}: nary atmospheric temperatures this form of the polymer is eithera viscousxliquid or a soft solid, but it can be rendered flowable by heating. The soluble andfusible polymer is capable of "being furthenpolymerizedeither alone or as it forms in 'admixture' with the monomer. Upon being further polymerized, the fusible polymer changes; to a gel form which isinsoluble in the common organic solvents including its monomer. Nevertheless, the insoluble gel is fusible and upon heating rendered fiowable.- Both the soluble polymerv and the fusible gel polymer are valuable materials for the 'usual resin molding operations eifecteol under heat'and pressure to form shaped ar'ticl'es because they still further polymerize t0 the final stage:'-"This final form of the polymer is insolublein common organic solvents as Well ""as being 'infusible." 'Uponheating the infusible polymer at -increasing temperatures, it finally reaches a temperature at which it decomposes, but intermediate between that temperature and room temperature, it does not become fusible or flowable although it-may soften slightly so as to "be capable of being bent or curved somewhat without brea'mn'g upon application of. stress. The? esters of the invention are thus seen to be titermosetting, resin-forming compounds and they pass through the three successive stages of polymerization to form first soluble polymer, then-insoluble gel polymer and finally infusible polymer.- While the intermediate polymeric forms can b'e obtained by interrupting the polymerization at a desired stage with separation of the polymer in the usual manner, the esters can be polymerized through to the final stage Without interruption'if desired. The interruption of the polymerization of the esters provides valuable mate-" rials for further processes. Incomplete polymerization can be used for the production of a syrup comprising a mixture of a monomer and fusiblepolymer which may be further worked and eveng tuall'y substantially completely polymerized. The syrup may for instance be transferred to mold of? any'des'ir'ed configuration and again subjected to polymerization conditions or it may housed in" coating operations or in impregnating bibulou's materials, such as paper, fabrics, -etc, whichim .ters. It isi'sometimes desirable to efiect the usually energized by the application of'heat al though both heat and-light may be used together and in some cases light alone is sufiicient. .Teinperatnres between about 60 C. and 150 C. are

preferred, although higher and lower temperatures can be used.

Like other diallyl and related esters, the compounds of the invention polymerize through three successive stages. Upon polymerizing a compo-- sition consisting of the ester, the soluble and',,

iusible form of the polymer isfirst produced This first polymer is ordinarily obtained in admixture with unpolymerized monomeric ester.

polymerization over a schedule involving varying "or increasing temperatures. Excellent results are obtained with the allyl esters by polymerizing with 2% benzoyl peroxide and heating 24 hours at C- then heating at C. for 6 hours, and completing-the curing at C. for an additional 18 hours.

The following examples illustrate the infnsible polymers for "a number of esters.

EXAMPLE XII Diallyl malate acetate prepared according to Example ILwas polymerized by heating at 65 7 "C. for fidays in the presence of 2% benzoyl perfl oxide. An optically clear polymer was obtained having a Barcol hardness of 45-50.

EXAMPLE XIII Y A sample of diallyl tartrate .diacetate prepared 7 EXAMP E XIV The infusiblepolymer of diallyl tartrate dipropionate preparedaccording to Example VII assessa- The stability of polymers-of the invention toward contact with water, dilute alkali and acid was determined for comparison with that of polymeric diallyl tartrate. This was determined by immersing weighed pieces of the polymer of the esters listed in the table below in the noted medium. After immersion for the indicated time, the pieces were again weighed. The percentage gain or loss in weight is given in the table. It

' will be notedfrom theresults that th polymers of the invention have excellent stability in each of the mediums while that of polymeric diallyl tartratef is inferior in stability against water and acid and three-quarters of the polymer disinwas obtained by heating in the presence of 2% 1 5- tegrated and disappeared in dilute alkali. I I Weightpercent change on submersion tests Mcdium-.. water 10% NaOH 3% mso.

Time 24 1 wk. 2 wks. 24 hrs. 1 wk. .lwks. 24 hrs. 1 wk. 2 wks.

Diallyl tartrate"; 0. 7 2.1 I 3.1 --l5. 7 66. 7 74. 9 O. 6 2.1 3.0 Diallyl tartrate diacetate" 0.5 1.3 1.6 0. 8 0.2 0. 5 0. 5 l. 3 1.6 Diallyl tartrate dipropiona 0.4 l. 0 l. l 0.3 0.3 0. l 0.3 0.8 0.9 Diallyl tartrate dibutyrate (1.6 0.6 0.6 0. 2 0.3 0.1 0.3 0.6 0.6

benzoyl peroxide at 65C. for 6 days. The clear polymer had a. Barcol hardness of 32.

Diallyl tartrate dibutyrate obtained as described in Example VIII-was polymerized at 65 C. for 6 days in the presence of 1% benzoyl per oxide. The clear infus.ble polymer had a Barcol hardness of 10-20.

EXAMPLE XVI The diallyl saccharate tetra-acetate obtained as reported in Example XI was polymerized by heating for 6 days at 65 C. in the presence of 5%.

benzoyl peroxide. The casting was clear with a Barcol hardness of 28-34.

, As was stated hereinbefore, the polymers of the invention possess a community of excellent physical properties. For' thepurposes of illus-' trating---thase-properties and comparing .them with closely related, known polymers,- the esters listed in the following table were polymerized 'to' the infusible state and the noted tests were.per-. formed upon them. It will be observed'from the? table that polymers of the invention have excellent strength and hardmss as shown by results.

of standard strength tests. Furthermore, their ability to transmit light is only slightly impaired Although the foregoing description has emphasized the homopolymers of the esters, copolymers are of value for many uses. The copoly- 30; mers can be formed from mixtures of two or olefinic linkage such as styrene, vinyl halides,

vinylidene halides, vinyl esters of saturated monocarboxylic acids, methyl acrylate, methyl methacrylate, allyl halides, allyl esters of satu-' rated monocarboxylic acids, etc. Another im- 40 portant group consists of unconjugated polymerratedpolyhydric alcohols with unsaturated organic acids, and esters of unsaturated'alcohols withun'saturated aliphatic acids. Other polymeri'zable'urisaturated compoundsare those containing'in the molecule one or more polymerizable organic radicalsand one or more inorganic radicals or elements as exemplified by the'vinyl, allyl and methallyl esters of phosphoric acid and of the ortho acids of silicon, boron, etc. Another important group of copolymerizable compounds consists of those having in the molecule two or more, preferably two, conjugated unsaturated polymerizable carbon-to-carbon linkages such as conjugated butadiene, conjugated chlorobutaand ability to transmit light.

V 1 e Diallyl Diall l Plgtlglllylt SDIRHYI fimllyl 3 Dmllyl 2 31 5 Tar-hate Tartr te I a as uccmate slate Acetate Tartrate Diacetate Dlpro- Dibutypionate rate Polymerization conditionsk fll I v A 1 A A A A A B 2 B Per cent benzoyl peroxide used 2 2 2 2 0 5 l 2 2 Barcol hardness. 0 8 0 49 42 49 41 26 Rockwell hardness, M sca1e 11,0 113 110 107 111 106 Tensile strength, lbs. per sq. in 7, 500 3, 600 4, 200 4, 200 Edgewise compression strength, lbs. per sq. 24 00 in ,0 3 00 21,. 000 23,000 2', 300 18 200 Flexturalstrength, lbs. per aq..1n 11, 200 8, 760 11, 000 18, 400 4: 300 Dynstat impact strength, kg. per sq. c l8 2.. 6. l 6.0 8.0 Per cent light. transmission at 425 mu ongrnaL 78 84 89 88 After 7 days southern exposure on roof.; 67 73 85 86 87 88 After 35 days southern exposure on meta 64 68 86 86 80 80 1 Heating at 65 0 for 144 hours.

- 2 Heating 24 hours at 65 0., 6 honrs at 90 QandlB hoursat C n mlolymeric diallyl succinate and diallyl malate had such low physi our m.

c al strength that the strength tests could not be performed diene, isoprene, the other conjugated pentadienes, the conjugated hexadienes, their homologues, analogues and suitable substitution products. Particularly valuable copolymers are those of the compounds of the invention with one or more allyl-type diesters of dicarboxylic acids containing in the molecule an ether linkage posi. tioned between the carboxy groups. An example of such ether-containing dicanboxylic acid esters is diallyl diglycolate.

We claim as our invention:

1. A diallyl ester of an acyloxylated aliphatic dicarboxylic acid, said acid having the carboxyl groups separated by a straight chain of up to six aliphatic carbon atoms to each of which is directly linked one acetyloxy radical.

2. An infusible polymer of the ester defined by claim 1.

3. A diallyl ester of a tartaric acid ester which has each of the hydroxy groups thereof esterified with a saturated fatty acid of not more than 4 carbon atoms.

4. An infusible polymer of a diallyl ester of a tartaric acid ester which has each of the hydroxy groups thereof esterified with a saturated fatty acid of not more than 4 carbon atoms.

5. Diallyl tartrate dipropionate.

6. An infusible polymer of diallyl tartrate propionate.

'7. Diallyl saccharate tetra-acetate.

8. An infusible polymer of diallyl saccharate tetra-acetate.

9. Diallyl tartrate diacetate.

10. A polymer of diallyl tartrate diacetate.

11. An infusible polymer of diallyl tartrate diacetate.

12. An ester of an acyloxylated aliphatic dicarboxylic acid having the hydrogen atom of each of the two carboxylic acid groups replaced by the hydrocarbon radical of a beta,gamma-monoolefinic monohydric alcohol of up to 6 carbon atoms, and said ester having the two carboxyl groups of said dicarboxylic acid separated by a straight chain of up to six aliphatic carbon atoms to each of which is directly linked one acyloxy radical of a saturated fatty acid of up to 4 carbon atoms.

13. A polymer of the ester defined by claim 12.

LYNWOOD N. WHIFIEI-IILL. EDWARD C. SI-IOKAL.

REFERENCES CITED The following references are of record in the file of this patent:

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12. AN ESTER OF AN ACYLOXYLATED ALIPHATIC DICARBOXYLIC ACID HAVING THE HYDROGEN ATOM OF EACH OF THE TWO CARBOXYLIC ACID GROUPS REPLACED BY THE HYDROCARBON RADICAL OF A BETA-GAMMA-MONOOLEFINIC MONOHYDRIC ALCOHOL OFUP TO 6 CARBON ATOMS, AND SAID ESTER HAVING THE TWO CARBOXYL GROUPS OF SAID DICARBOXYLIC ACID SEPARATED BY A STRAIGHT CHAIN OF UP TO SIX ALIPHATIC CARBON ATOMS TO EACH OF WHICH IS DIRECTLY LINKED ONE ACYLOXY RADICAL OF A SATURATED FATTY ACID OF UP TO 4 CARBON ATOMS. 